Detailed Description
In a first aspect, the present invention relates to a polyester molded article having a hard coating layer on at least a part of one surface, the polyester molded article having excellent scratch resistance and adhesion of the coating layer to the surface. In embodiments, a polyester article comprises a polyester composition comprising at least one polyester having a glycol component comprising residues of 1, 4-Cyclohexanedimethanol (CHDM) and/or 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD).
The term "residue" as used herein refers to any organic structure derived from the incorporation of the corresponding monomer into the polymer by polycondensation and/or esterification reactions. As used herein, the term "repeat unit" refers to an organic structure having dicarboxylic acid residues and diol residues bonded through a carbonyloxy group. Thus, for example, the dicarboxylic acid residues may be derived from dicarboxylic acid monomers or related acid halides, esters, salts, anhydrides, and/or mixtures thereof. Thus, as used herein, the term "dicarboxylic acid" is intended to include dicarboxylic acids and any derivatives of dicarboxylic acids, including their related acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and/or mixtures thereof, which can be used in a reaction process with a glycol to produce a copolyester. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and its residues as well as any derivatives of terephthalic acid, including the acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and/or mixtures thereof or residues thereof associated therewith, which can be used in a reaction process with a glycol to produce a copolyester.
In embodiments, a polyester molded article comprises a copolyester composition comprising at least one polyester comprising:
(a) A dicarboxylic acid component comprising:
i) 70mol% to 100mol% of terephthalic acid residues,
ii) from 0mol% to 30mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms, and
iii) From 0mol% to 10mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms;
and
(b) A glycol component comprising:
i) 10mol% to 99mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues and ii) 1mol% to 90mol% of 1, 4-cyclohexanedimethanol residues, wherein the total mol% of the dicarboxylic acid component is 100mol% and the total mol% of the diol component is 100mol%; and is also provided with
Wherein the inherent viscosity of the polyester is from 0.1 to 1.2dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃; and wherein T of the polyesterg 100-200 ℃.
In embodiments, a polyester molded article comprises a copolyester composition comprising at least one polyester comprising:
(a) A dicarboxylic acid component comprising:
i) 70mol% to 100mol% of terephthalic acid residues,
ii) from 0mol% to 30mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms, and
iii) From 0mol% to 10mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms;
and
(b) A glycol component comprising:
i) 15mol% to 70mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues and ii) 30mol% to 85mol% of 1, 4-cyclohexanedimethanol residues, wherein the total mol% of the dicarboxylic acid component is 100mol% and the total mol% of the diol component is 100mol%; and is also provided with
Wherein the inherent viscosity of the polyester is from 0.35 to 1.2dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃; and wherein T of the polyesterg Is 100-160 ℃.
In embodiments, a polyester molded article comprises a copolyester composition comprising at least one polyester comprising:
(a) A dicarboxylic acid component comprising:
i) 70mol% to 100mol% of terephthalic acid residues,
ii) from 0mol% to 30mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms, and
iii) From 0mol% to 10mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms;
and
(b) A glycol component comprising:
i) 20mol% to 40mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues and ii) 60mol% to 80mol% of 1, 4-cyclohexanedimethanol residues, wherein the total mol% of the dicarboxylic acid component is 100mol% and the total mol% of the diol component is 100mol%; and is also provided with
Wherein the inherent viscosity of the polyester is from 0.35 to 0.85dL/g, e.g., at 25 DEG C60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml; and wherein T of the polyesterg Is 100-120 ℃.
In embodiments, a polyester molded article comprises a copolyester composition comprising at least one polyester comprising:
(a) A dicarboxylic acid component comprising:
i) 70mol% to 100mol% of terephthalic acid residues,
ii) from 0mol% to 30mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms, and
iii) From 0mol% to 10mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms;
and
(b) A glycol component comprising:
i) 40mol% to 55mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues and ii) 45mol% to 60mol% of 1, 4-cyclohexanedimethanol residues, wherein the total mol% of the dicarboxylic acid component is 100mol% and the total mol% of the diol component is 100mol%; and is also provided with
Wherein the inherent viscosity of the polyester is from 0.35 to 0.85dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃; and wherein T of the polyesterg Is 120-140 ℃.
In embodiments, a polyester molded article comprises a copolyester composition comprising at least one polyester comprising:
(a) A dicarboxylic acid component comprising:
i) 70mol% to 100mol% of terephthalic acid residues,
ii) from 0mol% to 30mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms, and
iii) From 0mol% to 10mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms;
and
(b) A glycol component comprising:
i) 15mol% to 70mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues and ii) 30mol% to 85mol% of 1, 4-cyclohexanedimethanol residues, wherein the total mol% of the dicarboxylic acid component is 100mol% and the total mol% of the diol component is 100mol%; and
wherein the inherent viscosity of the polyester is from 0.35 to 0.85dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃; and wherein T of the polyesterg 100-140 ℃.
In embodiments, a polyester molded article comprises a copolyester composition comprising at least one polyester comprising:
(a) A dicarboxylic acid component comprising:
i) 70mol% to 100mol% of terephthalic acid residues,
ii) from 0mol% to 30mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms, and
iii) From 0mol% to 10mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms;
And
(b) A glycol component comprising:
i) 15mol% to 90mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues and ii) 10mol% to 85mol% of 1, 4-cyclohexanedimethanol residues, wherein the total mol% of the dicarboxylic acid component is 100mol% and the total mol% of the diol component is 100mol%; and is also provided with
Wherein the inherent viscosity of the polyester is from 0.1 to 1.2dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃; and wherein T of the polyesterg 100-200 ℃.
In embodiments, any of the polyesters or polyester compositions described herein may further comprise residues of at least one branching agent. In embodiments, any of the polyesters or polyester compositions described herein can comprise at least one heat stabilizer or reaction product thereof.
In embodiments, the polyester composition comprises at least one polycarbonate. In other embodiments, the polyester composition is free of polycarbonate.
In embodiments, polyesters useful in the present invention contain less than 15 mole% ethylene glycol residues, for example, from 0.01 mole% to less than 15 mole% ethylene glycol residues. In embodiments, polyesters useful in the present invention contain less than 10 mole%, or less than 5 mole%, or less than 4 mole%, or less than 2 mole%, or less than 1 mole% ethylene glycol residues, for example: 0.01mol% to less than 10mol%, or 0.01mol% to less than 5mol%, or 0.01mol% to less than 4mol%, or 0.01mol% to less than 2mol%, or 0.01mol% to less than 1mol% of ethylene glycol residues. In one embodiment, the polyesters useful in the present invention do not contain ethylene glycol residues.
Examples of higher EG residues:
in other embodiments, useful polyesters may include copolyesters comprising: (a) Diacid residues comprising about 90 mole% to 100 mole% TPA residues and 0 mole% to about 10 mole% IPA residues; and (b) glycol residues comprising at least 58 mole% EG residues and up to 42 mole% TMCD residues; wherein the copolyester comprises a total of 100 mole% diacid residues and a total of 100 mole% diol residues.
In embodiments, the copolyester comprises glycol residues comprising 5mol% to 42mol% TMCD residues and 58mol% to 95mol% EG residues. In one embodiment, the copolyester comprises glycol residues comprising 5 mole% to 40 mole% TMCD residues and 60 mole% to 95 mole% EG residues.
In embodiments, the copolyester comprises glycol residues comprising 20 mole% to 37 mole% TMCD residues and 63 mole% to 80 mole% EG residues. In one embodiment, the copolyester comprises glycol residues comprising 22 mole% to 35 mole% TMCD residues and 65 mole% to 78 mole% EG residues.
In an embodiment, the copolyester comprises: a) A dicarboxylic acid component comprising: (i) 90mol% to 100mol% of terephthalic acid residues, and (ii) about 0mol% to about 10mol% of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a glycol component comprising: (i) About 10 mole% to about 27 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues, and (ii) about 90 mole% to about 73 mole% ethylene glycol residues; and wherein the total mole% of the dicarboxylic acid component is 100 mole%, wherein the total mole% of the diol component is 100 mole%; and wherein the inherent viscosity (inherent viscosity, IV) of the polyester is from 0.50 to 0.8dL/g as measured at 25 ℃ in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25g/50 ml; and wherein the polyester has an L color value of 90 or greater as determined by the color system of L x a x b, as measured according to ASTM D6290-98 and ASTM E308-99, on polymer particles that are ground to pass through a 1mm screen. In an embodiment, the polyester has a color value L of greater than 90 as determined by the color system L a b, as measured according to ASTM D6290-98 and ASTM E308-99, on polymer particles that are ground to pass through a 1mm screen.
In certain embodiments, the glycol component of the copolyester comprises: (i) About 15 mole% to about 25 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and (ii) about 85 mole% to about 75 mole% ethylene glycol residues; alternatively, (i) from about 20 mole% to about 25 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and (ii) from about 80 mole% to about 75 mole% ethylene glycol residues; alternatively, (i) from about 21 mole% to about 24 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and (ii) from about 86 mole% to about 79 mole% ethylene glycol residues.
In one aspect, the copolyester comprises:
(a) A dicarboxylic acid component comprising:
(i) About 90 mole% to about 100 mole% of terephthalic acid residues,
(ii) About 0mol% to about 10mol% of aromatic and +.
Or aliphatic dicarboxylic acid residues; and
(b) A glycol component comprising:
(i) About 10 mole% to about 27 mole% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues, and
(ii) About 73 mole% to about 90 mole% of ethylene glycol residues, and
(iii) Less than about 5 mole%, or less than 2 mole% of any other modifying glycol;
wherein the total mole% of the dicarboxylic acid component is 100 mole%, and
wherein the total mole% of the glycol component is 100 mole%; and is also provided with
Wherein the inherent viscosity of the copolyester is from 0.50 to 0.8dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25g/50ml at 25 ℃.
In embodiments, the copolyester has at least one selected from the following characteristics: t (T)g From about 90 to about 108 ℃ -flexural modulus at 23 ℃ greater than about 2000MPa (290,000 psi) as measured by a TA 2100 thermal analyzer (Thermal Analyst Instrument) at a scan rate of 20 ℃/min-notched izod impact strength greater than about 25J/m (0.47 ft-lb/in) as defined by ASTM D790-measured at 23 ℃ with a 10 mil notch according to ASTM D256 using a 1/8 inch thick bar. In one embodiment, the polyester composition has an L color value of 90 or greater, or greater than 90, as determined by the L x a x b color system measured according to ASTM D6290-98 and ASTM E308-99, on polymer particles that are finely ground to pass through a 1mm screen.
In one embodiment, the copolyester further comprises: (II) a catalyst/stabilizer component comprising: (i) titanium atoms in the range of 10-50ppm based on the weight of the polymer, (ii) optionally manganese atoms in the range of 10-100ppm based on the weight of the polymer, and (iii) phosphorus atoms in the range of 10-200ppm based on the weight of the polymer. In one embodiment of the present invention, in one embodiment, the 2, 4-tetramethyl-1, 3-cyclobutanediol residues being those comprising greater than 50 mole% of cis-2, 4-tetramethyl-1, 3-cycles a mixture of butanediol residues and less than 50 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol residues.
In embodiments, the copolyesters useful in the present invention may be amorphous or semi-crystalline. In one embodiment, the copolyesters useful in the present invention may have relatively low crystallinity. In embodiments, the copolyesters useful in the present invention may thus have a substantially amorphous morphology, meaning that the polyesters comprise substantially disordered polymer regions.
In embodiments, the glycol component of the copolyester useful in the present invention may include, but is not limited to, at least one of the following combinations of ranges: about 10mol% to about 30mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and about 90mol% to about 70mol% of ethylene glycol; about 10mol% to about 27mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and about 90mol% to about 73mol% of ethylene glycol; about 15mol% to about 26mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and about 85mol% to about 74mol% of ethylene glycol; about 18mol% to about 26mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and about 82mol% to about 77mol% of ethylene glycol; about 20 mole% to about 25 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol and about 80 mole% to about 75 mole% ethylene glycol; about 21 mole% to about 24 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol and about 79 mole% to about 76 mole% ethylene glycol; or from about 22 mole% to about 24 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol and from about 78 mole% to about 76 mole% ethylene glycol.
In certain embodiments, the copolyesters useful in the present invention may exhibit at least one of the following inherent viscosities as measured at 25 ℃ in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25g/50 ml: 0.50-0.8dL/g;0.55-0.75dL/g;0.57-0.73dL/g;0.58-0.72dL/g;0.59-0.71dL/g;0.60-0.70dL/g;0.61-0.69dL/g;0.62-0.68dL/g;0.63-0.67dL/g;0.64-0.66dL/g; or about 0.65dL/g.
In certain embodiments, T of the copolyesterg May be selected from one of the following ranges: 85 to 100 ℃;86 to 99 ℃;87 to 98 ℃;88 to 97 ℃;89 to 96 ℃;90 to 95 ℃;91 to 95 ℃;92 to 94 ℃.
In another embodiment, the copolyester comprises glycol residues comprising 30 mole% to 42 mole% TMCD residues and 58 mole% to 70 mole% EG residues. In one embodiment, the copolyester comprises glycol residues comprising 33 mole% to 38 mole% TMCD residues and 62 mole% to 67 mole% EG residues.
In an embodiment, the copolyester comprises: a) A dicarboxylic acid component comprising (i) 90 to 100 mole% of terephthalic acid residues and (ii) about 0 to about 10 mole% of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a glycol component comprising (i) about 30 mole% to about 42 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and (ii) about 70 mole% to about 58 mole% ethylene glycol residues; and wherein the total mole% of the dicarboxylic acid component is 100 mole%, and wherein the total mole% of the diol component is 100 mole%; and wherein the Inherent Viscosity (IV) of the polyester is from 0.50 to 0.70dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25g/50ml at 25 ℃; and wherein the polyester has an L color value of 90 or greater as determined by the color system of L x a x b, as measured according to ASTM D6290-98 and ASTM E308-99, on polymer particles that are ground to pass through a 1mm screen. In an embodiment, the polyester has a color value L of greater than 90 as determined by the color system L a b, as measured according to ASTM D6290-98 and ASTM E308-99, on polymer particles that are ground to pass through a 1mm screen.
In certain embodiments, the glycol component comprises: (i) About 32 mole% to about 42 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues, and (ii) about 68 mole% to about 58 mole% ethylene glycol residues; alternatively, (i) from about 34 mole% to about 40 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues, and (ii) from about 66 mole% to about 60 mole% ethylene glycol residues; alternatively, (i) from greater than 34 mole% to about 40 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues, and (ii) from less than 66 mole% to about 60 mole% ethylene glycol residues; alternatively, (i) 34.2 mole% to about 40 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues, and (ii) 65.8 mole% to about 60 mole% ethylene glycol residues; alternatively, (i) from about 35 mole% to about 39 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues, and (ii) from about 65 mole% to about 61 mole% ethylene glycol residues; alternatively, (i) from about 36 mole% to about 37 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues, and (ii) from about 64 mole% to about 63 mole% ethylene glycol residues.
In one embodiment, the copolyester comprises:
(a) A dicarboxylic acid component comprising:
(i) About 90 mole% to about 100 mole% of terephthalic acid residues,
(ii) From about 0mol% to about 10mol% of aromatic and/or aromatic groups having up to 20 carbon atoms
Aliphatic dicarboxylic acid residues; and
(b) A glycol component comprising:
(i) About 30 mole% to about 42 mole% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues, and
(ii) About 70 mole% to about 58 mole% of ethylene glycol residues, and
(iii) Less than about 5 mole%, or less than 2 mole% of any other modifying glycol;
wherein the total mole% of the dicarboxylic acid component is 100 mole%, and
wherein the total mole% of the glycol component is 100 mole%; and is also provided with
Wherein the inherent viscosity of the polyester is from 0.50 to 0.70dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25g/50ml at 25 ℃.
In embodiments, the copolyester has at least one selected from the following characteristics: t (T)g From about 100 to about 110 ℃ -flexural modulus at 23 ℃ equal to or greater than 2000MPa (about 290,000 psi) or greater than 2200MPa (319,000 psi) as measured by a TA2100 thermal analyzer at a scan rate of 20 ℃/min-notched izod impact strength as defined by ASTM D790 is from about 30J/m (0.56 ft-lb/in) to about 80J/m (1.50 ft-lb/in) -as measured according to ASTM D256 using a 1/8 inch thick rod with a 10 mil notch at 23 ℃ and an inherent viscosity loss of less than 5% after 2 minutes holding at a temperature of 293 ℃ (560°f). In one embodiment, the polyester composition has an L color value of 90 or greater, or greater than 90, as determined by the L x a x b color system measured according to ASTM D6290-98 and ASTM E308-99, on polymer particles that are finely ground to pass through a 1mm screen.
In one embodiment, the copolyester comprises a glycol component having at least 30 mole% TMCD residues (based on glycol) and a catalyst/stabilizer component comprising: (i) titanium atoms in the range of 10 to 60ppm based on the weight of the polymer, (ii) manganese atoms in the range of 10 to 100ppm based on the weight of the polymer, and (iii) phosphorus atoms in the range of 10 to 200ppm based on the weight of the polymer. In one embodiment of the present invention, in one embodiment, the 2, 4-tetramethyl-1, 3-cyclobutanediol residues being those comprising greater than 50 mole% of cis-2, 4-tetramethyl-1, 3-cycles a mixture of butanediol residues and less than 50 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol residues.
In embodiments, the glycol component of the copolyester used in the present invention includes, but is not limited to, at least one of the following combinations of ranges: about 30 mole% to about 42 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol and about 58 mole% to about 70 mole% ethylene glycol; about 32 mole% to about 42 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol and about 58 mole% to about 68 mole% ethylene glycol; about 32 mole% to about 38 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol and about 64 mole% to about 68 mole% ethylene glycol; about 33 mole% to about 41 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol and about 59 mole% to 67 mole% ethylene glycol; about 34 mole% to about 40 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol and about 60 mole% to about 66 mole% ethylene glycol; more than 34 mole% to about 40 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol and 60 mole% to less than 66 mole% ethylene glycol; 34.2mol% to 40mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and about 60mol% to 65.8mol% of ethylene glycol; about 35 mole% to about 39 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol and about 61 mole% to 65 mole% ethylene glycol; about 35 mole% to about 38 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol and about 62 mole% to about 65 mole% ethylene glycol; or about 36 mole% to about 37 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol and about 63 mole% to about 64 mole% ethylene glycol.
In certain embodiments, polyesters useful in the present invention may exhibit at least one of the following inherent viscosities as measured at 25 ℃ in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25g/50 ml: 0.50-0.70dL/g;0.55-0.65dL/g;0.56-0.64dL/g;0.56-0.63dL/g;0.56-0.62dL/g;0.56-0.61dL/g;0.57-0.64dL/g;0.58-0.64dL/g;0.57-0.63dL/g;0.57-0.62dL/g;0.57-0.61dL/g;0.58-0.60dL/g or about 0.59dL/g.
In certain embodiments of copolyesters having higher EG residues, such copolyesters contain CHDM residues in the following levels: less than 10 mole%, or less than 5 mole%, or less than 4 mole%, or less than 3 mole%, or less than 2 mole%, or less than 1 mole%, or no CHDM residues.
Additional embodiments applicable to any or all of the embodiments disclosed herein:
in the examples, the polyesters useful in the present invention are not prepared from 1, 3-propanediol or 1, 4-butanediol, either alone or in combination. In other aspects, 1, 3-propanediol or 1, 4-butanediol, alone or in combination, can be used to prepare polyesters useful in the present invention.
In embodiments, in some polyesters useful in the present invention, the mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol useful is greater than 50 mole%, or greater than 55 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol, or greater than 70 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol; wherein the total mole percent of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and trans-2, 4-tetramethyl-1, 3-cyclobutanediol is equal to 100 mole percent of the total.
In the examples, among certain polyesters useful in the present invention, the mole% of isomers of 2, 4-tetramethyl-1, 3-cyclobutanediol that are useful are: 30 to 70mol% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol, or 30 to 70mol% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol, or 40 to 60mol% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol, or from 40 to 60mol% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol, wherein the total mole percent of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and trans-2, 4-tetramethyl-1, 3-cyclobutanediol is equal to 100 mole percent of the total.
In embodiments, the polyester compositions may be used in ophthalmic products including, but not limited to, extruded and/or molded articles including, but not limited to, injection molded articles, extruded articles, cast extruded articles. Furthermore, in one embodiment, the use of the polyester composition of the present invention minimizes and/or eliminates the drying step prior to melt processing or thermoforming.
In embodiments, certain polyesters useful in the present invention may be amorphous or semi-crystalline. In one aspect, certain polyesters useful in the present invention may have relatively low crystallinity. Thus, certain polyesters useful in the present invention may have a substantially amorphous morphology, meaning that the polyesters comprise substantially disordered polymer regions.
It is believed that polyesters and/or polyester compositions included in hard coat coated polyester articles (e.g., ophthalmic products) as described herein may have a unique combination of two or more physical properties such as high impact strength, medium to high glass transition temperature, chemical resistance, hydrolytic stability, toughness (toughess), low ductile to brittle transition temperature (low-to-brittle transition temperature), good color and clarity, low density, long semicrystalline time, and good processability to readily make them into articles. In some embodiments of the invention, the polyester has a unique combination of the following characteristics: good impact strength, heat resistance, chemical resistance, density, and/or a combination of the following properties: good impact strength, heat resistance and processability, and/or combinations of two or more of the described characteristics, which have not previously been considered to be present in ophthalmic products comprising polyester compositions comprising the polyesters disclosed herein.
In embodiments, the hard-coated polyester article is an ophthalmic product. As used herein, "ophthalmic product" refers to prescription ophthalmic lenses, non-prescription ophthalmic lenses, sunglass lenses, and eyeglass and sunglass frames. In one embodiment, the ophthalmic product is selected from the group consisting of colored ophthalmic lenses and hard-coated ophthalmic lenses. In one embodiment, an ophthalmic lens, such as a colored ophthalmic lens or a hard-coated ophthalmic lens, comprises at least one polarizing film or polarizing additive. In one embodiment, when the product is a lens, the refractive index of the ophthalmic product ranges from 1.54 to 1.56. In one embodiment, the ophthalmic product may have at least one property selected from the group consisting of: toughness, clarity, chemical resistance (e.g., for resistance to lens cleaners, oils, hair products, etc.), Tg And hydrolytic stability.
The term "polyester" as used herein is intended to include "copolyesters" and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and/or polyfunctional carboxylic acids with one or more difunctional hydroxyl compounds and/or polyfunctional hydroxyl compounds. Typically, the difunctional carboxylic acid may be a dicarboxylic acid and the difunctional hydroxyl compound may be a dihydric alcohol, such as a glycol. Furthermore, as used herein, the term "diacid" or "dicarboxylic acid" includes polyfunctional acids, such as branching agents. The term "glycol" or "diol" as used herein includes, but is not limited to, diols (diols, glycols) and/or polyfunctional hydroxy compounds. Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid such as parahydroxybenzoic acid and the difunctional hydroxyl compound may be an aromatic nucleus bearing 2 hydroxyl substituents such as hydroquinone. The term "residue" as used herein refers to any organic structure derived from the incorporation of the corresponding monomer into the polymer by polycondensation and/or esterification reactions. As used herein, the term "repeat unit" refers to an organic structure having dicarboxylic acid residues and diol residues bonded through a carbonyloxy group. Thus, for example, the dicarboxylic acid residues may be derived from dicarboxylic acid monomers or related acid halides, esters, salts, anhydrides, or mixtures thereof. Thus, as used herein, the term dicarboxylic acid is intended to include dicarboxylic acids and any derivative of dicarboxylic acids, including the relevant acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, which can be used in a reaction process with a glycol to produce a polyester. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and its residues as well as any derivatives of terephthalic acid, including the acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof or residues thereof associated therewith, which can be used in a reaction process with a glycol to produce a polyester.
In one embodiment, terephthalic acid may be used as the starting material. In another embodiment, dimethyl terephthalate may be used as the starting material. In another embodiment, a mixture of terephthalic acid and dimethyl terephthalate may be used as the starting material and/or intermediate material.
The polyesters useful in the present invention can generally be prepared from dicarboxylic acids and diols that are reacted in substantially equal proportions and incorporated into the polyester polymer at their corresponding residues. Thus, the polyesters of the invention may contain substantially equal molar proportions of acid residues (100 mole%) and glycol (and/or polyfunctional hydroxy compound) residues (100 mole%) such that the total moles of repeating units is equal to 100 mole%. Thus, the mole percentages provided in the present disclosure may be based on the total moles of acid residues, the total moles of glycol residues, or the total moles of repeat units. For example, a polyester containing 30 mole% isophthalic acid based on the total acid residues means that the polyester contains 30 mole% isophthalic acid residues of the total of 100 mole% acid residues. Thus, 30 moles of isophthalic acid residues are present per 100 moles of acid residues. In another example, the polyester contains 30 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol based on total diol residues, meaning that the polyester contains 30 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol residues, based on total 100 mole% diol residues. Thus, there are 30 moles of 2, 4-tetramethyl-1, 3-cyclobutanediol residues per 100 moles of diol residues.
In the examples, T is the polyester used in the articles of the inventiong May be at least one of the following ranges: 100 to 200 ℃;100 to 190 ℃;100 to 180 ℃;100 to 170 ℃;100 to 160 ℃;100 to 155 ℃;100 to 150 ℃;100 to 145 ℃;100 to 140 ℃;100 to 138 ℃;100 to 135 ℃;100 to 130 ℃;100 to 125 ℃;100 to 120 ℃;100 to 115 ℃;100 to 110 ℃;105 to 200 ℃;105 to 190 ℃;105 to 180 ℃;105 to 170 ℃;105 to 160 ℃;105 to 155 ℃;105 to 150 ℃;105 to 145 ℃;105 to 140 ℃;105 to 138 ℃;105 to 135 ℃;105 to 130 ℃;105 to 125 ℃;105 to 120 ℃;105 to 115 ℃;105 to 110 ℃; greater than 105 to 125 ℃; greater than 105 to 120 ℃; greater than 105 to 115 ℃; greater than 105 to 110 ℃;110 to 200 ℃;110 to 190 ℃;110 to 180 ℃;110 to 170 ℃;110 to 160 ℃;110 to 155 ℃;110 to 150 ℃;110 to 145 ℃;110 to 140 ℃;110 to 138 ℃;110 to 135 ℃;110 to 130 ℃;110 to 125 ℃;110 to 120 ℃;110 to 115 ℃;115 to 200 ℃;115 to 190 ℃;115 to 180 ℃;115 to 170 ℃;115 to 160 ℃;115 to 155 ℃;115 to 150 ℃;115 to 145 ℃;115 to 140 ℃;115 to 138 ℃;115 to 135 ℃;110 to 130 ℃;115 to 125 ℃;115 to 120 ℃;120 to 200 ℃;120 to 190 ℃;120 to 180 ℃;120 to 170 ℃;120 to 160 ℃;120 to 155 ℃;120 to 150 ℃;120 to 145 ℃;120 to 140 ℃;120 to 138 ℃;120 to 135 ℃;120 to 130 ℃;125 to 200 ℃;125 to 190 ℃;125 to 180 ℃;125 to 170 ℃;125 to 160 ℃;125 to 155 ℃;125 to 150 ℃;125 to 145 ℃;125 to 1 40 ℃;125 to 138 ℃;125 to 135 ℃;127 to 200 ℃;127 to 190 ℃;127 to 180 ℃;127 to 170 ℃;127 to 160 ℃;127 to 150 ℃;127 to 145 ℃;127 to 140 ℃;127 to 138 ℃;127 to 135 ℃;130 to 200 ℃;130 to 190 ℃;130 to 180 ℃;130 to 170 ℃;130 to 160 ℃;130 to 155 ℃;130 to 150 ℃;130 to 145 ℃;130 to 140 ℃;130 to 138 ℃;130 to 135 ℃;135 to 200 ℃;135 to 190 ℃;135 to 180 ℃;135 to 170 ℃;135 to 160 ℃;135 to 155 ℃;135 to 150 ℃;135 to 145 ℃;135 to 140 ℃;140 to 200 ℃;140 to 190 ℃;140 to 180 ℃;140 to 170 ℃;140 to 160 ℃;140 to 155 ℃;140 to 150 ℃;140 to 145 ℃;148 to 200 ℃;148 to 190 ℃;148 to 180 ℃;148 to 170 ℃;148 to 160 ℃;148 to 155 ℃;148 to 150 ℃;150 to 200 ℃;150 to 190 ℃;150 to 180 ℃;150 to 170 ℃;150 to 160 ℃;155 to 190 ℃;155 to 180 ℃;155 to 170 ℃; and 155 to 165 ℃.
In embodiments, the glycol component of the polyesters used in the ophthalmic products of the present invention include, but are not limited to, at least one of the following combinations of ranges: 10mol% to 99mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 1mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 95mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 5mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 90mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 10mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 85mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 15mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 80mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 20mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 75mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 25mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 70mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 30mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 65mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 35mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 60mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 40mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 55mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 45mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 50mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 50mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to less than 50mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and greater than 50mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 45mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 55mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 40mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 60mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 35mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 65mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to less than 35mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and more than 65mol% to at most 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 30mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 70mol% to 90mol% of 1, 4-cyclohexanedimethanol; 10mol% to 25mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and greater than 75mol% to 90mol% of 1, 4-cyclohexanedimethanol; 11mol% to 25mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 75mol% to 89mol% of 1, 4-cyclohexanedimethanol; 12mol% to 25mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 75mol% to 88mol% of 1, 4-cyclohexanedimethanol; and 13mol% to 25mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 75mol% to 87mol% of 1, 4-cyclohexanedimethanol.
In other embodiments, the glycol component of the polyesters used in the ophthalmic products of the present invention include, but are not limited to, at least one of the following combinations of ranges: 14mol% to 99mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 1mol% to 86mol% of 1, 4-cyclohexanedimethanol; 14mol% to 95mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 5mol% to 86mol% of 1, 4-cyclohexanedimethanol; 14mol% to 90mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 10mol% to 86mol% of 1, 4-cyclohexanedimethanol; 14mol% to 85mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 15mol% to 86mol% of 1, 4-cyclohexanedimethanol; 14mol% to 80mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 20mol% to 86mol% of 1, 4-cyclohexanedimethanol; 14mol% to 75mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 25mol% to 86mol% of 1, 4-cyclohexanedimethanol; 14mol% to 70mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 30mol% to 86mol% of 1, 4-cyclohexanedimethanol; 14mol% to 65mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 35mol% to 86mol% of 1, 4-cyclohexanedimethanol; 14mol% to 60mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 40mol% to 86mol% of 1, 4-cyclohexanedimethanol; 14mol% to 55mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 45mol% to 86mol% of 1, 4-cyclohexanedimethanol; and, 14mol% to 50mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 50mol% to 86mol% of 1, 4-cyclohexanedimethanol.
In other embodiments, the glycol component of the polyesters used in the ophthalmic products of the present invention include, but are not limited to, at least one of the following combinations of ranges: 15mol% to 99mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 1mol% to 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 95mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 5mol% to 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 90mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 10mol% to 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 85mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 15mol% to 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 80mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 20mol% to 85mol% of 1, 4-cyclohexanedimethanol, 15mol% to 75mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 25mol% to 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 70mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 30mol% to 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 65mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 35mol% to 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 60mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 40mol% to 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 55mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 45mol% to 85mol% of 1, 4-cyclohexanedimethanol; and 15mol% to 50mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 50mol% to 85mol% of 1, 4-cyclohexanedimethanol.
In other embodiments, the glycol component of the polyesters used in the ophthalmic products of the present invention include, but are not limited to, at least one of the following combinations of ranges: 15mol% to less than 50mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and more than 50mol% to at most 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 45mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 55mol% to 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 40mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 60mol% to 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 35mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 65mol% to 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 30mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 70mol% to 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 25mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 75mol% to 85mol% of 1, 4-cyclohexanedimethanol; 15mol% to 20mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 75mol% to 80mol% of 1, 4-cyclohexanedimethanol; and 17mol% to 23mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 77mol% to 83mol% of 1, 4-cyclohexanedimethanol.
In other embodiments, the glycol component of the polyesters used in the ophthalmic products of the present invention include, but are not limited to, at least one of the following combinations of ranges: 20mol% to 99mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 1mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 95mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 5mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 90mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 10mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 85mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 15mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 80mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 20mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 75mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 25mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 70mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 30mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 65mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 35mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 60mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 40mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 55mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 45mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 50mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 50mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 45mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 55mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 40mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 60mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 35mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 65mol% to 80mol% of 1, 4-cyclohexanedimethanol; 20mol% to 30mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 70mol% to 80mol% of 1, 4-cyclohexanedimethanol; and 20mol% to 25mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 75mol% to 80mol% of 1, 4-cyclohexanedimethanol.
In other embodiments, the glycol component of the polyesters used in the ophthalmic products of the present invention include, but are not limited to, at least one of the following combinations of ranges: 25mol% to 99mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 1mol% to 75mol% of 1, 4-cyclohexanedimethanol; 25mol% to 95mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 5mol% to 75mol% of 1, 4-cyclohexanedimethanol; 25mol% to 90mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 10mol% to 75mol% of 1, 4-cyclohexanedimethanol; 25mol% to 85mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 15mol% to 75mol% of 1, 4-cyclohexanedimethanol; 25mol% to 80mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 20mol% to 75mol% of 1, 4-cyclohexanedimethanol; 25mol% to 75mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 25mol% to 75mol% of 1, 4-cyclohexanedimethanol; 25mol% to 70mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 30mol% to 75mol% of 1, 4-cyclohexanedimethanol; 25mol% to 65mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 35mol% to 75mol% of 1, 4-cyclohexanedimethanol; 25mol% to 60mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 40mol% to 75mol% of 1, 4-cyclohexanedimethanol; 25mol% to 55mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 45mol% to 75mol% of 1, 4-cyclohexanedimethanol; 25mol% to 50mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 50mol% to 75mol% of 1, 4-cyclohexanedimethanol; 25mol% to 45mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 55mol% to 75mol% of 1, 4-cyclohexanedimethanol; 25mol% to 40mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 60mol% to 75mol% of 1, 4-cyclohexanedimethanol; 25mol% to 35mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 65mol% to 75mol% of 1, 4-cyclohexanedimethanol; and 25mol% to 30mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 70mol% to 75mol% of 1, 4-cyclohexanedimethanol.
In other embodiments, the glycol component of the polyesters used in the ophthalmic products of the present invention include, but are not limited to, at least one of the following combinations of ranges: 30mol% to 99mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 1mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30mol% to 95mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 5mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30mol% to 90mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 10mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30mol% to 85mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 15mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30mol% to 80mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 20mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30mol% to 75mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 25mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30mol% to 70mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 30mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30mol% to 65mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 35mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30mol% to 60mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 40mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30mol% to 55mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 45mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30mol% to 50mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 50mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30mol% to less than 50mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and greater than 50mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30mol% to 45mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 55mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30mol% to 40mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 60mol% to 70mol% of 1, 4-cyclohexanedimethanol; 30 to 35mol% of 2, 4-tetramethyl-1, 3-cyclobutanediol and 65 to 70mol% of 1, 4-cyclohexanedimethanol.
In addition to the diols set forth above, polyesters useful in the polyester compositions of the ophthalmic products of the present invention may also be prepared from 1, 3-propanediol, 1, 4-butanediol, or mixtures thereof. It is contemplated to use 1, 3-propanediol, 1, 4-butanediol, or a mixture thereofThe compositions of the invention prepared from the mixtures may have T as described hereing At least one of the ranges, at least one of the inherent viscosity ranges described herein, and/or at least one of the diol or diacid ranges described herein. Additionally or alternatively, polyesters prepared from 1, 3-propanediol or 1, 4-butanediol or mixtures thereof may also be made from 1, 4-cyclohexanedimethanol in at least one of the following amounts: 0.1mol% to 99mol%;0.1mol% to 90mol%;0.1mol% to 80mol%;0.1mol% to 70mol%;0.1mol% to 60mol%;0.1mol% to 50mol%;0.1mol% to 40mol%;0.1mol% to 35mol%;0.1mol% to 30mol%;0.1mol% to 25mol%;0.1mol% to 20mol%;0.1mol% to 15mol%;0.1mol% to 10mol%;0.1mol% to 5mol%;1mol% to 99mol%;1mol% -90mol%, 1mol% -80mol%;1mol% to 70mol%;1mol% to 60mol%;1mol% to 50mol%;1mol% to 40mol%;1mol% to 35mol%;1mol% to 30mol%;1mol% to 25mol%;1mol% to 20mol%;1mol% to 15mol%;1mol% to 10mol%;1mol% to 5mol%;5mol% to 99mol%;5mol% to 90mol%;5mol% to 80mol%;5mol% to 70mol%;5mol% to 60mol%;5mol% to 50mol%;5mol% to 40mol%;5mol% to 35mol%;5mol% to 30mol%;5mol% to 25mol%;5mol% to 20mol%; and 5mol% to 15mol%;5mol% to 10mol%;10mol% to 99mol%;10mol% to 90mol%;10mol% to 80mol%;10mol% to 70mol%;10mol% to 60mol%;10mol% to 50mol%;10mol% to 40mol%;10mol% to 35mol%;10mol% to 30mol%; 10mol% to 25mol%;10mol% to 20mol%;10mol% to 15mol%;20mol% to 99mol%;20mol% to 90mol%;20mol% to 80mol%;20mol% to 70mol%;20mol% to 60mol%;20mol% to 50mol%;20mol% to 40mol%;20mol% to 35mol%;20mol% to 30mol%; and, 20mol% to 25mol%.
For certain embodiments, polyesters useful in the present invention may exhibit at least one of the following inherent viscosities as measured at 25 ℃ in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml: 0.10-1.2dL/g;0.10-1.1dL/g;0.10-1dL/g; 0.10-less than 1dL/g;0.10-0.98dL/g;0.10-0.95dL/g;0.10-0.90dL/g;0.10-0.85dL/g;0.10-0.80dL/g;0.10-0.75dL/g; 0.10-less than 0.75dL/g;0.10-0.72dL/g;0.10-0.70dL/g; 0.10-less than 0.70dL/g;0.10-0.68dL/g; 0.10-less than 0.68dL/g;0.10-0.65dL/g;0.20-1.2dL/g;0.20-1.1dL/g;0.20-1dL/g; 0.20-less than 1dL/g;0.20-0.98dL/g;0.20-0.95dL/g;0.20-0.90dL/g;0.20-0.85dL/g;0.20-0.80dL/g;0.20-0.75dL/g; 0.20-less than 0.75dL/g;0.20-0.72dL/g;0.20-0.70dL/g; 0.20-less than 0.70dL/g;0.20-0.68dL/g; 0.20-less than 0.68dL/g;0.20-0.65dL/g;0.35-1.2dL/g;0.35-1.1dL/g;0.35-1dL/g; 0.35-less than 1dL/g;0.35-0.98dL/g;0.35-0.95dL/g;0.35-0.90dL/g;0.35-0.85dL/g;0.35-0.80dL/g;0.35-0.75dL/g; 0.35-less than 0.75dL/g;0.35-0.72dL/g;0.35-0.70dL/g; 0.35-less than 0.70dL/g;0.35-0.68dL/g; 0.35-less than 0.68dL/g;0.35-0.65dL/g;0.40-1.2dL/g;0.40-1.1dL/g;0.40-1dL/g; 0.40-less than 1dL/g;0.40-0.98dL/g;0.40-0.95dL/g;0.40-0.90dL/g;0.40-0.85dL/g;0.40-0.80dL/g;0.40-0.75dL/g;0.40 to less than 0.75dL/g;0.40-0.72dL/g;0.40-0.70dL/g; 0.40-less than 0.70dL/g;0.40-0.68dL/g; 0.40-less than 0.68dL/g;0.40-0.65dL/g; greater than 0.42-1.2dL/g; greater than 0.42-1.1dL/g; greater than 0.42-1dL/g; greater than 0.42 and less than 1dL/g; greater than 0.42-0.98dL/g; greater than 0.42-0.95dL/g; greater than 0.42-0.90dL/g; greater than 0.42-0.85dL/g; greater than 0.42-0.80dL/g; greater than 0.42-0.75dL/g; greater than 0.42 and less than 0.75dL/g; greater than 0.42-0.72dL/g; greater than 0.42 and less than 0.70dL/g; greater than 0.42-0.68dL/g; greater than 0.42 and less than 0.68dL/g; and greater than 0.42-0.65dL/g.
For certain embodiments, polyesters useful in the present invention may exhibit at least one of the following inherent viscosities as measured at 25 ℃ in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml: 0.45-1.2dL/g;0.45-1.1dL/g;0.45-1dL/g;0.45-0.98dL/g;0.45-0.95dL/g;0.45-0.90dL/g;0.45-0.85dL/g;0.45-0.80dL/g;0.45-0.75dL/g; 0.45-less than 0.75dL/g;0.45-0.72dL/g;0.45-0.70dL/g; 0.45-less than 0.70dL/g;0.45-0.68dL/g; 0.45-less than 0.68dL/g;0.45-0.65dL/g;0.50-1.2dL/g;0.50-1.1dL/g;0.50-1dL/g; 0.50-less than 1dL/g;0.50-0.98dL/g;0.50-0.95dL/g;0.50-0.90dL/g;0.50-0.85dL/g;0.50-0.80dL/g;0.50-0.75dL/g; 0.50-less than 0.75dL/g;0.50-0.72dL/g;0.50-0.70dL/g; 0.50-less than 0.70dL/g;0.50-0.68dL/g; 0.50-less than 0.68dL/g;0.50-0.65dL/g;0.55-1.2dL/g;0.55-1.1dL/g;0.55-1dL/g; 0.55-less than 1dL/g;0.55-0.98dL/g;0.55-0.95dL/g;0.55-0.90dL/g;0.55-0.85dL/g;0.55-0.80dL/g;0.55-0.75dL/g; 0.55-less than 0.75dL/g;0.55-0.72dL/g;0.55-0.70dL/g; 0.55-less than 0.70dL/g;0.55-0.68dL/g; 0.55-less than 0.68dL/g;0.55-0.65dL/g;0.58-1.2dL/g;0.58-1.1dL/g;0.58-1dL/g; 0.58-less than 1dL/g;0.58-0.98dL/g;0.58-0.95dL/g;0.58-0.90dL/g;0.58-0.85dL/g;0.58-0.80dL/g;0.58-0.75dL/g; 0.58-less than 0.75dL/g;0.58-0.72dL/g;0.58-0.70dL/g; 0.58-less than 0.70dL/g;0.58-0.68dL/g; 0.58-less than 0.68dL/g;0.58-0.65dL/g;0.60-1.2dL/g;0.60-1.1dL/g;0.60-1dL/g; 0.60-less than 1dL/g;0.60-0.98dL/g;0.60-0.95dL/g;0.60-0.90dL/g;0.60-0.85dL/g;0.60-0.80dL/g;0.60-0.75dL/g; 0.60-less than 0.75dL/g;0.60-0.72dL/g;0.60-0.70dL/g; 0.60-less than 0.70dL/g;0.60-0.68dL/g; 0.60-less than 0.68dL/g;0.60-0.65dL/g;0.65-1.2dL/g;0.65-1.1dL/g;0.65-1dL/g; 0.65-less than 1dL/g;0.65-0.98dL/g;0.65-0.95dL/g;0.65-0.90dL/g;0.65-0.85dL/g;0.65-0.80dL/g;0.65-0.75dL/g; 0.65-less than 0.75dL/g;0.65-0.72dL/g;0.65-0.70dL/g; 0.65-less than 0.70dL/g;0.68-1.2dL/g;0.68-1.1dL/g;0.68-1dL/g; 0.68-less than 1dL/g;0.68-0.98dL/g;0.68-0.95dL/g;0.68-0.90dL/g;0.68-0.85dL/g;0.68-0.80dL/g;0.68-0.75dL/g; 0.68-less than 0.75dL/g;0.68-0.72dL/g; greater than 0.76dL/g to 1.2dL/g; greater than 0.76dL/g to 1.1dL/g; greater than 0.76dL/g-1dL/g; greater than 0.76dL/g and less than 1dL/g; greater than 0.76dL/g to 0.98dL/g; greater than 0.76dL/g to 0.95dL/g; greater than 0.76dL/g to 0.90dL/g; greater than 0.80dL/g to 1.2dL/g; greater than 0.80dL/g to 1.1dL/g; greater than 0.80dL/g to 1dL/g; greater than 0.80dL/g and less than 1dL/g; greater than 0.80dL/g to 1.2dL/g; greater than 0.80dL/g to 0.98dL/g; greater than 0.80dL/g to 0.95dL/g; greater than 0.80dL/g to 0.90dL/g.
Unless otherwise indicated, compositions contemplated for use in articles (e.g., ophthalmic products) may have at least one of the inherent viscosity ranges described herein and at least one of the monomer ranges of the compositions described herein. It is also contemplated that, unless otherwise indicated, may be used in the presentThe composition of the inventive article may have T as described hereing At least one of the ranges neutralizes at least one of the monomer ranges of the compositions described herein. It is also contemplated that, unless otherwise indicated, compositions useful in the ophthalmic products of the present invention may have T as described hereing At least one of the ranges, at least one of the inherent viscosity ranges described herein, and at least one of the monomer ranges of the compositions described herein.
In embodiments, the molar ratio of cis/trans 2, 4-tetramethyl-1, 3-cyclobutanediol may be different from the respective pure forms or mixtures thereof. In certain embodiments, the mole percentages of cis and/or trans 2, 4-tetramethyl-1, 3-cyclobutanediol are: more than 50mol% cis and less than 50mol% trans; or greater than 55 mole% cis and less than 45 mole% trans; or 30mol% to 70mol% cis and 70mol% to 30mol% trans; or 40mol% to 60mol% cis and 60mol% to 40mol% trans; or 50mol% to 70mol% trans and 50mol% to 30mol% cis; or 50mol% to 70mol% cis and 50mol% to 30mol% trans; or 60mol% to 70mol% cis and 30mol% to 40mol% trans; or greater than 70 mole% cis and less than 30 mole% trans; wherein the sum of the mole percentages of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and trans-2, 4-tetramethyl-1, 3-cyclobutanediol is equal to 100 mole%. The molar ratio of cis/trans 1, 4-cyclohexanedimethanol may vary from 50/50 to 0/100, for example between 40/60 and 20/80.
In certain embodiments, terephthalic acid or an ester thereof (e.g., dimethyl terephthalate), or a mixture of terephthalic acid and an ester thereof, comprises a majority or all of the dicarboxylic acid component used to form the polyesters useful in the present invention. In certain embodiments, terephthalic acid residues may comprise a portion or all of the dicarboxylic acid component used to form the polyesters of the invention in a concentration of: at least 70mol%, such as at least 80mol%, at least 90mol%, at least 95mol%, at least 99mol%, or 100mol%. In certain embodiments, a greater amount of terephthalic acid may be used to produce a higher impact polyester. In one embodiment, the dimethyl terephthalate is part or all of the dicarboxylic acid component used to make the polyesters useful in the present invention. For the purposes of this disclosure, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. In all embodiments, the following ranges of terephthalic acid and/or dimethyl terephthalate and/or mixtures thereof may be used: 70mol% to 100mol%; or 80mol% to 100mol%; or 90mol% to 100mol%; or 99mol% to 100mol%; or 100mol%.
In addition to terephthalic acid, the dicarboxylic acid component of the polyesters useful in the present invention may comprise up to 30 mole%, up to 20 mole%, up to 10 mole%, up to 5 mole%, or up to 1 mole% of one or more modified aromatic dicarboxylic acids. Another embodiment contains 0 mole% of the modified aromatic dicarboxylic acid. Thus, if present, it is contemplated that the amount of the one or more modified aromatic dicarboxylic acids may be within any of these aforementioned endpoints, including, for example, 0.01mol% to 30mol%, 0.01mol% to 20mol%, 0.01mol% to 10mol%, 0.01mol% to 5mol%, and 0.01mol% to 1mol%. In one embodiment, the modified aromatic dicarboxylic acids useful in the present invention include, but are not limited to, those having up to 20 carbon atoms, and which may be linear, para-oriented, or symmetrical. Examples of modified aromatic dicarboxylic acids useful in the present invention include, but are not limited to: isophthalic acid, 4 '-biphenyldicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, and trans-4, 4' -stilbenedicarboxylic acid, and esters thereof. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.
The carboxylic acid component of the polyesters useful in the present invention may be further modified with up to 10 mole percent, for example up to 5 mole percent or up to 1 mole percent, of one or more aliphatic dicarboxylic acids containing 2 to 16 carbon atoms, such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and dodecanedioic acid. Certain embodiments may also comprise 0.01mol% or more (e.g., 0.1mol% or more, 1mol% or more, 5mol% or more, or 10mol% or more) of one or more modified aliphatic dicarboxylic acids. Yet another embodiment contains 0 mole% of the modified aliphatic dicarboxylic acid. Thus, if present, it is contemplated that the amount of the one or more modified aliphatic dicarboxylic acids may be within any of these aforementioned end-point values, including, for example, 0.01 mole% to 10 mole% and 0.1 mole% to 10 mole%. The total mole% of the dicarboxylic acid component is 100 mole%.
Instead of dicarboxylic acids, esters of terephthalic acid and other modified dicarboxylic acids or their corresponding esters and/or salts may be used. Suitable examples of dicarboxylic acid esters include, but are not limited to, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the ester is selected from at least one of the following: methyl, ethyl, propyl, isopropyl and phenyl esters.
The 1, 4-cyclohexanedimethanol may be cis, trans or mixtures thereof, for example in a cis/trans ratio of 60:40 to 40:60. In another embodiment, trans-1, 4-cyclohexanedimethanol may be present in an amount of from 60 mole% to 80 mole%.
The glycol component of the polyester portion of the polyester composition useful in the present invention may contain 25 mole% or less of one or more modified diols that are not 2, 4-tetramethyl-1, 3-cyclobutanediol or 1, 4-cyclohexanedimethanol; in one embodiment, the polyesters useful in the present invention may contain less than 15 mole% of one or more modifying diols. In another embodiment, the polyesters useful in the present invention may contain 10 mole% or less of one or more modifying diols. In another embodiment, the polyesters useful in the present invention may contain 5 mole% or less of one or more modifying diols. In another embodiment, the polyesters useful in the present invention may contain 3 mole% or less of one or more modifying diols. In another embodiment, the polyesters useful in the present invention may contain 0 mole% of the modified diol. Certain embodiments may also contain 0.01mol% or more of one or more modifying diols, for example 0.1mol% or more, 1mol% or more, 5mol% or more, or 10mol% or more. Thus, if present, it is contemplated that the amount of one or more modifying diols may be within any of these aforementioned endpoints, including, for example, 0.01mol% to 15mol% and 0.1mol% to 10mol%.
The modified diols useful in the polyesters useful in the present invention refer to diols other than 2, 4-tetramethyl-1, 3-cyclobutanediol and 1, 4-cyclohexanedimethanol, and may contain from 2 to 16 carbon atoms. Examples of suitable modifying diols include, but are not limited to: ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, neopentyl glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, terephthalyl alcohol, or mixtures thereof. In one embodiment, the modified diol is ethylene glycol. In another embodiment, the modified diol is 1, 3-propanediol and/or 1, 4-butanediol. In another embodiment, ethylene glycol is excluded as the modifying glycol. In another embodiment, 1, 3-propanediol and 1, 4-butanediol are excluded as the modifying diols. In another embodiment, 2-dimethyl-1, 3-propanediol is excluded as the modifying diol.
The polyesters and/or polycarbonates (if included) useful in the polyester compositions of the present invention may comprise, based on the total mole percent of diol or diacid residues, from 0 mole percent to 10 mole percent (e.g., from 0.01 mole percent to 5 mole percent, from 0.01 mole percent to 1 mole percent, from 0.05 mole percent to 5 mole percent, from 0.05 mole percent to 1 mole percent, or from 0.1 mole percent to 0.7 mole percent), respectively, of residues of one or more branching monomers, also referred to herein as branching agents, having 3 or more carboxyl substituents, hydroxyl substituents, or combinations thereof. In certain embodiments, the branching monomer or branching agent may be added before and/or during and/or after polymerization of the polyester. Thus, the polyesters useful in the present invention may be linear or branched. The polycarbonates may also be linear or branched. In certain embodiments, the branching monomer or branching agent may be added before and/or during and/or after polymerization of the polycarbonate.
Examples of branching monomers include, but are not limited to, polyfunctional acids or alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylol propane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, and the like. In one embodiment, the branching monomer residues may comprise from 0.1 mole% to 0.7 mole% of one or more residues selected from at least one of the following: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2, 6-hexanetriol, pentaerythritol, trimethylolethane and/or pyromellitic acid. The branching monomers may be added to the polyester reaction mixture or blended with the polyester in the form of a concentrate, such as described in U.S. Pat. nos. 5,654,347 and 5,696,176, the disclosures of which are incorporated herein by reference for branching monomers.
Glass transition temperature (T) of polyesters useful in the present inventiong ) Measured using a TA DSC 2920 from thermal analysis instruments (Thermal Analyst Instrument) at a scan rate of 20 ℃/min.
Certain polyesters useful in the present invention exhibit long semicrystalline times (e.g., greater than 5 minutes) at 170 ℃ allowing the production of injection molded ophthalmic products, compression molded ophthalmic products, and solution cast ophthalmic products. The polyesters of the invention may be amorphous or semi-crystalline. In one aspect, certain polyesters useful in the present invention may have relatively low crystallinity. Thus, certain polyesters useful in the present invention may have a substantially amorphous morphology, meaning that the polyesters comprise substantially disordered polymer regions.
In one embodiment, the semi-crystallization time of an "amorphous" polyester may be greater than 5 minutes at 170 ℃, or greater than 10 minutes at 170 ℃, or greater than 50 minutes at 170 ℃, or greater than 100 minutes at 170 ℃. In one embodiment of the invention, the semi-crystallization time is greater than 1,000 minutes at 170 ℃. In another embodiment of the invention, the semi-crystallization time of the polyesters useful in the present invention is greater than 10,000 minutes at 170 ℃. As used herein, the semicrystalline time of a polyester can be measured using methods well known to those skilled in the art. For example, the half crystallization time (t)1/2 ) The determination can be made by: the light transmittance of the sample was measured as a function of time by a laser and photodetector on a temperature controlled hotplate. The measurement may be made by: exposing the polymer to a temperature Tmax It is then cooled to the desired temperature. The sample can then be held at the desired temperature by a hot stage while transmission measurements are made as a function of time. Initially, the sample may be visually transparent, have high light transmittance, and become opaque as the sample crystallizes. The half-crystallization time is the time that the light transmittance is halfway between the initial transmission and the final transmission. T (T)max Defined as the temperature required to melt the domains of the sample (if present). The sample may be heated to T before measuring the crystallization half timemax To condition the sample. Absolute T for each compositionmax The temperatures are different. For example, PCT may be heated to a temperature greater than 290 ℃ to melt the domains.
In embodiments, certain polyesters useful in the present invention are visually transparent. The term "visually transparent" is defined herein as clearly free of clouds (clouding), haze (hazing) and/or haze (muddiness) when visually inspected. In one aspect of the invention, when the polyester is blended with polycarbonate (including bisphenol a polycarbonate), the blend may be visually clear. The polyesters of the invention may have one or more of the following properties. In other embodiments, the yellowness index (ASTM D-1925) of the polyesters useful in the present invention may be less than 50, such as less than 20.
In examples, polyesters useful in the present invention and/or the polyester compositions of the present invention, whether or not containing a toner, can have color values L, a, and b, which can be measured using Hunter Lab overscan colorimeter (Ultrascan Spectra Colorimeter) manufactured by Hunter combined laboratory inc (Hunter Associates Lab inc., reston, va), of leston, usa. The color measurement is an average value measured on polyester pellets, plaques, or other articles injection molded or extruded from them. They are determined by the color system of CIE (International Commission on Illumination ) (translation) L x a x b x, where L x represents the luminance coordinates, a x the red/green coordinates, and b x the yellow/blue coordinates. In certain embodiments, the polyesters useful in the present invention can have b values of from-10 to less than 10 and l values of from 50 to 90. In other embodiments, the b values for the polyesters of the invention may exist in one of the following ranges: -10 to 9; -10 to 8; -10 to 7; -10 to 6; -10 to 5; -10 to 4; -10 to 3; -10 to 2; from-5 to 9; -5 to 8; -5 to 7; -5 to 6; -5 to 5; -5 to 4; -5 to 3; -5 to 2;0 to 9;0 to 8;0 to 7;0 to 6;0 to 5;0 to 4;0 to 3;0 to 2;1 to 10;1 to 9;1 to 8;1 to 7;1 to 6;1 to 5;1 to 4;1 to 3; and 1 to 2. In other embodiments, the L values for the polyesters of the invention may exist in one of the following ranges: 50 to 60;50 to 70;50 to 80;50 to 90;60 to 70;60 to 80;60 to 90;70 to 80;79 to 90.
The polyester fraction which can be used in the polyester compositions of the invention can be prepared by processes known in the literature, for example by processes in homogeneous solutions, by transesterification processes in the melt and by two-phase interfacial processes. Suitable methods include those disclosed in U.S. published application 2006/0287484, the contents of which are incorporated herein by reference.
In an embodiment, the polyester may be prepared by a process comprising reacting one or more dicarboxylic acids with one or more diols under conditions that provide the polyester, including, but not limited to, the steps of: the one or more dicarboxylic acids are reacted with the one or more diols at a temperature of 100 ℃ to 315 ℃ and a pressure of 0.1 to 760mmHg for a time sufficient to form the polyester. See U.S. Pat. No. 3,772,405, the disclosure of which is incorporated herein by reference, for a process for producing polyesters.
In an embodiment, the polyester composition may be a polymer blend, wherein the blend comprises: (a) 5wt% to 95wt% of at least one polyester described above; and (b) 5wt% to 95wt% of at least one polymer component. Suitable examples of polymer components include, but are not limited to: nylon, polyesters other than those described herein, polyamides such as those from DuPont (DuPont)Polystyrene, polystyrene copolymers, styrene acrylonitrile copolymers, acrylonitrile butadiene styrene copolymers, poly (methyl methacrylate), acrylic acid copolymers, poly (ether-imide) s, for example +.>(poly (ether-imide) s available from General Electric); polyphenylene ethers, such as poly (2, 6-dimethyl-phenyl ether) or poly (phenyl ether)/polystyrene blends, such as NORYL +>(blends of poly (2, 6-dimethyl-phenyl ether) and polystyrene resins from general electric); polyphenylene sulfide; polyphenylene sulfide/sulfone; poly (ester-carbonate); polycarbonates, e.g.>(polycarbonates from general electric); polysulfone; polysulfone ether; and poly (ether-ketone) of aromatic dihydroxy compounds; or a mixture of any of the other aforementioned polymers. The blends may be prepared by conventional processing techniques known in the art, such as melt blending or solution blending. In one embodiment, no polycarbonate is present in the polyester composition. If a polycarbonate is used in the blend useful in the polyester compositions of the present invention, the blend may be visually clear. However, the polyester compositions useful in the present invention are also contemplated to exclude polycarbonates and include polycarbonates. / >
In addition, the polyester compositions and polymer blend compositions useful in the articles of the present invention may also contain from 0.01wt% to 25wt% of the total composition of conventional additives such as colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers (including but not limited to ultraviolet stabilizers, heat stabilizers and/or reaction products thereof), fillers and impact modifiers. For example, the uv additive may be incorporated into an article (e.g., an ophthalmic product) by being added to the body or in a hard coating. Examples of typical commercially available impact modifiers well known in the art and useful in the present invention include, but are not limited to: ethylene/propylene terpolymers; functionalized polyolefins, such as those containing methyl acrylate and/or glycidyl methacrylate; styrene-based block copolymer impact modifiers; and various acrylic core/shell impact modifiers. Residues of these additives are also contemplated as part of the polyester composition.
In embodiments, the polyesters of the invention may comprise at least one chain extender. Suitable chain extenders include, but are not limited to, polyfunctional (including, but not limited to difunctional) isocyanates, polyfunctional epoxides including, for example, epoxidized novolacs and phenoxy resins. In certain embodiments, the chain extender may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extender may be introduced by way of mixing (compounding) or addition during the conversion process (e.g., injection molding or extrusion). The amount of chain extender used may vary depending on the particular monomer composition used and the physical properties desired, but is generally from 0.1wt% to 10wt%, for example from 0.1wt% to 5wt%, based on the total weight of the polyester.
Heat stabilizers are compounds that stabilize polyesters during their manufacture and/or after polymerization, including but not limited to phosphorus compounds including but not limited to phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonite, and various esters and salts thereof. The esters may be alkyl esters, branched alkyl esters, substituted alkyl esters, difunctional alkyl esters, alkyl ether esters, aryl esters and substituted aryl esters. In one embodiment, the number of ester groups present in a particular phosphorus compound may vary from zero to up to the maximum allowed based on the number of hydroxyl groups present on the heat stabilizer used. The term "heat stabilizer" is intended to include the reaction products thereof. The term "reaction product" as used in connection with the heat stabilizer of the present invention refers to: any product of polycondensation or esterification reaction between a heat stabilizer and any monomer used to make the polyester, and between a catalyst and any other type of additive. These may be present in the polyester compositions useful in the present invention.
Reinforcing materials may be used in the compositions of the present invention. Reinforcing materials may include, but are not limited to: carbon filaments, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flake, glass beads and fibers, and polymeric fibers, and combinations thereof. In one embodiment, the reinforcing material is glass, for example: fiber glass filaments, mixtures of glass and talc, mixtures of glass and mica, and mixtures of glass and polymer fibers.
In certain embodiments, the hard-coat coated article relates to an ophthalmic product described herein. Such ophthalmic products include, but are not limited to, injection molded ophthalmic products, compression molded ophthalmic products, and solution cast ophthalmic products. Methods of manufacturing ophthalmic products include, but are not limited to, injection molding, compression molding, and solution casting.
In an embodiment, the hard coating is applied to the surface of the polyester article as a solvent-based liquid coating comprising 1wt% to 50wt% solids and 50wt% to 99wt% solvent system based on the total weight of the coating. In an embodiment, the hard coating is a one-component (i.e., single layer) liquid coating system. In embodiments, the hardcoat is one-part and thermally cured in a one-step process, thereby providing a more efficient process compared to two-part systems and two-step curing processes. In embodiments, the polyester article has a single layer (or single component) hard coating with good adhesion and scratch resistance without the need for any primer or adhesion layer, or any additional top coat, for example, to further improve scratch resistance. In embodiments, the thickness of the (cured) monolayer hardcoat is 2-20, or 2-15, or 2-10, or 2-8, or 4-20, or 4-15, or 4-10, or 4-8 microns.
In an embodiment, the solvent system comprises an adhesion-enhancing solvent component in an amount of at least 10wt% based on the total weight of the liquid coating. In embodiments, the adhesion enhancing solvent component is present in an amount of at least 15wt%, or 20wt%, or 25wt%, or 30wt%, or 35wt%, or 40wt%, or 45wt%, or 50wt%, based on the total weight of the liquid coating. In an embodiment, the adhesion enhancing solvent component is present in an amount in the following range, based on the total weight of the liquid coating: 10wt% to 75wt%, or 10wt% to 70wt%, or 10wt% to 65wt%, or 10wt% to 60wt%, or 10wt% to 55wt%, or 10wt% to 50wt%, or 10wt% to 45wt%, or 10wt% to 40wt%, or 15wt% to 75wt%, or 15wt% to 70wt%, or 15wt% to 65wt%, or 15wt% to 60wt%, or 15wt% to 55wt%, or 15wt% to 50wt%, or 15wt% to 45wt%, or 15wt% to 40wt%, or 20wt% to 75wt%, or 20wt% to 70wt%, or 20wt% to 65wt%, or 20wt% to 60wt%, or 20wt% to 55wt%, or 20wt% to 50wt%, or 20wt% to 45wt%, or 20wt% to 40wt%, or 25wt% to 75wt%, or 25wt% to 60wt%, or 25wt% to 55wt%, or 25wt% to 50wt%, or 25wt% to 45wt%, or 25wt% to 40wt%, or 30wt% to 75wt%, or 30wt% to 65wt%, or 30wt% to 60wt%, or 30wt% to 55 wt%.
In an embodiment, the adhesion enhancing solvent component comprises a solvent selected from the group consisting of: methoxy-2-Propanol (PM), ethylene glycol butyl Ether (EB), or a combination of PM and EB. In an embodiment, the PM: the weight ratio of EB is greater than 1:1, or is within the following range: 1.01:1 to 10:1, or 1.1:1 to 10:1, or 1.2:1 to 5:1, or 1.2:1 to 4.5:1.
The hard coat coated polyester article may be prepared by: at least a portion of one surface of the article is coated with a hard coat coating composition (where hard coat function is desired) and the coating composition is cured. In embodiments, the coating composition may comprise a silicone alcohol resin/colloidal silica dispersion, such as those described in US20060287484, US10000588, and US 8163850. In an embodiment, a hard coating composition comprises a silicone alcohol resin, a colloidal silica dispersion, one or more curing catalysts, an adhesion-enhancing solvent component, and one or more other solvents.
The hard coating composition may be applied to the polyester article by any suitable method including, but not limited to: by brushing, by roller coating, by spraying, by dipping, etc. Curing may be accomplished by any suitable curing mechanism, including, for example, thermal curing.
In embodiments, the coating composition may comprise one or more silicone alcohol resins, such as, but not limited to: organotrialkoxysilanes and organodialkoxysilanes, tetraethoxysilane, ethyltriethoxysilane, diethyldiethoxysilane, tetramethoxysilane, methyltrimethoxysilane and dimethyldimethoxysilane. Examples of commercially available silicone alcohol resins include: EDN920 (available from DON), silFORT PHC XH100P and SilFORT SHC300 (available from Momentive) and EWL918/100/200 (available from Winlight).
In embodiments, the coating composition may include one or more crosslinking catalysts, such as NACURE 155, K-CURE 1040, K-CURE 129B, NACURE XP-357 (available from King Industries). In embodiments, the coating composition may be thermally cured at a low temperature in the range of 80-120 ℃.
In an embodiment, the coating composition may be prepared by: a hard coating solid material (e.g., a silicone alcohol resin), an adhesion-enhancing solvent component, and optionally one or more other solvents. In embodiments, the adhesion enhancing solvent component may be a preformed material that is added to the preformed coating liquid to provide the final coating composition, or the adhesion enhancing solvent component may be incorporated into the original coating composition during formation of the coating composition. That is, the components used to form the adhesion-promoting solvent component may be added to the coating material, and the adhesion-promoting solvent component may be formed as part of the reaction process for curing the coating composition.
In embodiments, the hard coating further comprises one or more adhesion promoters. In embodiments, the adhesion promoter has a hydroxyl number of from about 20 to about 300mg KOH/g polyester. Examples of useful adhesion promoters include: tetrashield IC3020 (available from Eastman Chemical), K-Flex188 (available from King's industry), P1110 (available from Macroocean).
In an embodiment, the hard coating composition comprises an adhesion enhancing solvent component and one or more other solvents. In embodiments, adhesion enhancing solvent components and other solvents are used: 1) Diluting the silicone alcohol resin; and 2) etching the surface of the polyester article to a degree to improve the adhesion of the hardcoat. In an embodiment, the adhesion enhancing solvent component comprises: methoxy-2-Propanol (PM), optionally ethylene glycol butyl Ether (EB); and the other solvent may be an alcohol such as methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, ethylene glycol, or mixtures thereof. In other embodiments, the other solvent may be a water miscible organic solvent such as acetone, methyl ethyl ketone, ethylene glycol monopropyl ether, 2-butoxyethanol, and/or diacetone alcohol. In an embodiment, the solvent component (including the adhesion-enhancing solvent component and one or more other solvents) of the hard coating composition comprises: methoxy-2-propanol, and at least one of 2-butoxyethanol and/or diacetone alcohol or a mixture thereof. In one embodiment, the solvent component of the hard coating composition comprises: methoxy-2-Propanol (PM), ethylene glycol butyl Ether (EB), and at least one of 2-butoxyethanol and/or diacetone alcohol or a mixture thereof.
In one aspect, a method of improving a single coat hard coat layer on a polyester article is provided, wherein the method comprises: providing a single coat hard coating composition comprising an adhesion enhancing solvent component, and coating at least a portion of a surface of the polyester article with the hard coating composition; wherein the adhesion-enhancing solvent component comprises methoxy-2-Propanol (PM) and ethylene glycol butyl Ether (EB) in amounts such that the combined weight of PM and EB is 10wt% or more based on the total weight of the hard coating composition, and PM: EB is greater than 1:1, and wherein the polyester article comprises a polyester composition comprising a polyester having TMCD residues.
In an embodiment, the adhesion enhancing solvent component comprises methoxy-2-Propanol (PM) and ethylene glycol butyl Ether (EB) in amounts such that the combined weight of PM and EB, based on the total weight of the hard coating composition, is: at least 10wt%, or 20wt%, or 30wt%, or 40wt%, or 50wt%, or 60wt%, or 70wt%, or 75wt%, or more. In an embodiment, the combined weight of PM and EB, based on the total weight of the liquid coating, is: 10wt% to 75wt%, or 10wt% to 70wt%, or 10wt% to 65wt%, or 10wt% to 60wt%, or 10wt% to 55wt%, or 10wt% to 50wt%, or 10wt% to 45wt%, or 10wt% to 40wt%, or 15wt% to 75wt%, or 15wt% to 70wt%, or 15wt% to 65wt%, or 15wt% to 60wt%, or 15wt% to 55wt%, or 15wt% to 50wt%, or 15wt% to 45wt%, or 15wt% to 40wt%, or 20wt% to 75wt%, or 20wt% to 70wt%, or 20wt% to 65wt%, or 20wt% to 60wt%, or 20wt% to 55wt%, or 20wt% to 50wt%, or 20wt% to 45wt%, or 20wt% to 40wt%, or 25wt% to 75wt%, or 25wt% to 70wt%, or 25wt% to 65wt% of or 25wt% to 60wt%, or 25wt% to 55wt%, or 25wt% to 50wt%, or 25wt% to 45wt%, or 25wt% to 40wt%, or 30wt% to 75wt%, or 30wt% to 70wt%, or 30wt% to 65wt%, or 30wt% to 60wt%, or 30wt% to 55wt%, or 30wt% to 50wt%, or 30wt% to 45wt%, or 30wt% to 40wt%, or 40wt% to 75wt%, or 40wt% to 70wt%, or 40wt% to 65wt%, or 40wt% to 60wt%, or 40wt% to 55wt%, or 40wt% to 50wt%, or 50wt% to 75wt%, or 50wt% to 70wt%, or 50wt% to 65wt%, or 50wt% to 60wt%, or 55wt% to 75wt%, or 55wt% to 70wt%, or 55wt% to 65wt%.
In an embodiment, the PM is present in an amount based on the total weight of the hard coating composition of: at least 5wt%, or 6wt%, or 7wt%, or 8wt%, or 9wt%, or 10wt%, or 15wt%, or 20wt%, or 25wt%, or 30wt%, or 35wt%, or 40wt%, or 45wt%, or 50wt%, or more. In an embodiment, the PM is present in an amount in the following range, based on the total weight of the hard coating composition: 5wt% to 60wt%, or 6wt% to 60wt%, or 7wt% to 60wt%, or 8wt% to 60wt%, or 9wt% to 60wt%, or 10wt% to 60wt%, or 15wt% to 60wt%, or 20wt% to 60wt%, or 25wt% to 60wt%, or 30wt% to 60wt%, or 35wt% to 60wt%, or 40wt% to 60wt%, or 45wt% to 60wt%, or 50wt% to 60wt%, or 5wt% to 55wt%, or 6wt% to 55wt%, or 7wt% to 55wt%, or 8wt% to 55wt%, or 9wt% to 55wt%, or 10wt% to 55wt%, or 15wt% to 55wt%, or 20wt% to 55wt%, or 25wt% to 55wt%, or 30wt% to 55wt%, or 35wt% to 55wt%, or 40wt% to 55wt%, or 45wt% to 55wt%, or 50wt% to 55wt%, or 5wt% to 20wt%, or 5wt% to 15wt%, or 5wt% to 10wt%, or 20wt% to 50wt%, or 25wt% to 55wt%, or 30wt% to 40wt%. In an embodiment, the PM: the weight ratio of EB is greater than 1:1, or 1.1:1, or 1.2:1. In an embodiment, the PM: the weight of EB is in the following range: 1.1:1-5:1, or 1.2:1-4:1, or 1.2:1-3:1, or 1.2:1-2:1, or 1.2:1-1.5:1, or 1.2:1-1.4:1, or 2:1-5:1, or 2:1-4.5:1, or 2:1-4:1, or 2:1-3.5:1, or 2.5:1-5:1, or 2.5:1-4.5:1, or 2.5:1-4:1, or 2.5:1-3.5:1, or 3:1-4.5:1, or 3:1-3.5:1.
For the purposes of this disclosure, the term "wt" refers to "weight".
While the following examples are provided to specifically and in detail illustrate many aspects and advantages of the present invention, they should not be construed as limiting its scope in any way. Variations, modifications, and adaptations of the present invention will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention.
Examples
Hard coat coated lenses were prepared by coating injection molded polyester sunglass lenses with various single layer liquid hard coat systems, and the resulting hard coat coated lenses were evaluated.
The materials used are as follows:
polyester material:
VX351HF copolyester (from Isman chemical company)
Starting silanol hard coating material:
EM300: liquid paint (from Momentive)
EDN rating: liquid paint (from DON company)
EWL class: liquid paint (from Winlight company)
Solvent:
ethylene glycol butyl Ether (EB), S.G.0.902 liquid solvent
methoxy-2-Propanol (PM), S.G.0.923 liquid solvent
Hard coat coated lens samples for testing were prepared as follows:
1. injection molding a copolyester sunglass lens;
2. the surface of the molded lenses was treated by immersing in 10-15% NaOH solution at 60 ℃ for 20 minutes, and then washing with ethanol and pure water;
3. Some starting silanol hard coating materials are modified by replacing the solvents originally present with different amounts of EB and PM solvents to provide modified silanol hard coating compositions;
4. then dip coating the lens with a different silanol hard coating composition;
5. the treated lenses were air dried at about 60-70 ℃ for about 10 minutes and then cured in an air circulation oven at about 95 ℃ for 3-6 hours. A hard coat coated lens with an optically clear coating is obtained with a coating layer having a thickness of 2-8 microns.
The adhesion and scratch resistance of the resulting silanol hard coated polyester article was then evaluated using the following test procedure:
(1) Hot water resistance test
The water immersion test was performed by placing a given sample in 80 ℃ water for one hour. During the soaking period, the sample was completely covered with water and was not allowed to contact the heated bottom of the container. After the soak period, the samples were removed from the water and cooled to room temperature before the adhesion test was performed.
(2) Adhesion test
The equipment and test procedure used were as follows: adhesion was measured according to ASTM D3359-17 (cross-hatch adhesion). The coated test specimen was scored with a razor blade and cut through the coating to form a series of score lines in a 100 mm square area, the lines forming a 1mm square. Scotch tape (3 m 810) was applied to the scribe surface, pressed down, and then peeled off sharply in a direction perpendicular to the test panel surface. The number of blocks remaining intact on the sample is reported as a percentage of the total number of blocks on the grid. The results were classified as 0B to 5B, 0B being worst (greater than 65% drop), 1B 35% -65% drop, 2B 15% -35% drop, 3B 5% -15% drop, 4B less than 5% drop, 5B being the best adhesion strength (no drop).
(3) Scratch resistance test
Scratch resistance tests were performed using 0000# steel wool. Four layers of steel wool were applied, placed into a 250g hammer groove, and the steel wool was exposed to the exterior of the hammer. The coated sample blanks were tested for scratch resistance in the center of the sample by dragging the steel wool under a weight for 30 cycles. The hammer is gripped by the end of its handle so that most of the pressure on the steel wool comes from the hammer head. The samples were classified according to the amount of scratch produced by steel wool and hammer. The samples were rated for no scratches, 1 grade, 2 grade for slight scratches, and 3 grade for severe scratches. The results were classified as follows by percentage of area containing 3-grade scratches or higher: 100% of the area is scratched to 1 level; 75% of the area was scratched to grade 2; 50% of the area was scratched to grade 3; 25% of the area was scratched to grade 4; 0% of the area was scratched to the best 5-level.
The polyester articles were characterized by using the following analytical techniques:
the Inherent Viscosity (IV) of the polyesters is determined at 25℃in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml.
Melting Point (T)m ) And glass transition temperature (T)g ) Measured by a differential scanning calorimeter (differential scanning calorimeter, DSC) type Q2000 using a TA instrument at a scan rate of 20 ℃/min.
The coating composition, polyester properties and test results are listed in table 1 below:
table 1: primer-free hard coating adhesion test
* The article was kept at room temperature for 24 hours after water treatment at 80 ℃ for 1 hour before cross-hatch testing according to ASTM 3359.
A review of table 2 shows that the use of sufficient amounts of PM and EB solvents in the hard coating results in improved adhesion and scratch resistance.
The foregoing description of various embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Many modifications and variations are possible in light of the above teaching. The embodiments discussed were chosen and described to provide the best illustration of the principles of the invention and its practical application to thereby enable one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally and equitably entitled.